JP4530616B2 - Devices using polythiophenes - Google Patents
Devices using polythiophenes Download PDFInfo
- Publication number
- JP4530616B2 JP4530616B2 JP2003006210A JP2003006210A JP4530616B2 JP 4530616 B2 JP4530616 B2 JP 4530616B2 JP 2003006210 A JP2003006210 A JP 2003006210A JP 2003006210 A JP2003006210 A JP 2003006210A JP 4530616 B2 JP4530616 B2 JP 4530616B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- polythiophenes
- polythiophene
- film transistor
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000123 polythiophene Polymers 0.000 title claims description 74
- 239000010409 thin film Substances 0.000 claims description 49
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000010410 layer Substances 0.000 description 59
- 239000004065 semiconductor Substances 0.000 description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- -1 oligoarylene Chemical group 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229920001940 conductive polymer Polymers 0.000 description 7
- 239000000976 ink Substances 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 125000005556 thienylene group Chemical group 0.000 description 7
- 125000000732 arylene group Chemical group 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- YNZKCHBXBASBJT-UHFFFAOYSA-N 3,4-dioctyl-2,5-dithiophen-2-ylthiophene Chemical compound CCCCCCCCC=1C(CCCCCCCC)=C(C=2SC=CC=2)SC=1C1=CC=CS1 YNZKCHBXBASBJT-UHFFFAOYSA-N 0.000 description 5
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 125000005567 fluorenylene group Chemical group 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000005647 linker group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000004377 microelectronic Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010129 solution processing Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- BNXJIUWYGDXAOL-UHFFFAOYSA-N 2,5-bis(5-bromothiophen-2-yl)-3,4-dioctylthiophene Chemical compound CCCCCCCCC=1C(CCCCCCCC)=C(C=2SC(Br)=CC=2)SC=1C1=CC=C(Br)S1 BNXJIUWYGDXAOL-UHFFFAOYSA-N 0.000 description 3
- WAOUDPOLPWAIGN-UHFFFAOYSA-N 3,4-dioctylthiophene Chemical compound CCCCCCCCC1=CSC=C1CCCCCCCC WAOUDPOLPWAIGN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 125000005560 phenanthrenylene group Chemical group 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- HTYVENFRAWYMAH-UHFFFAOYSA-N 2,5-dibromo-3,4-dioctylthiophene Chemical compound CCCCCCCCC1=C(Br)SC(Br)=C1CCCCCCCC HTYVENFRAWYMAH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- VGKLVWTVCUDISO-UHFFFAOYSA-N 3,4-dibromothiophene Chemical compound BrC1=CSC=C1Br VGKLVWTVCUDISO-UHFFFAOYSA-N 0.000 description 1
- QKHDNXHDVJABLD-UHFFFAOYSA-N 3,4-dioctyl-2-thiophen-2-ylthiophene Chemical compound CCCCCCCCC1=CSC(C=2SC=CC=2)=C1CCCCCCCC QKHDNXHDVJABLD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CMNLPODXHQFPBG-UHFFFAOYSA-N C[Si](N[Si](C)(C)C)(C)C.ClCCl Chemical compound C[Si](N[Si](C)(C)C)(C)C.ClCCl CMNLPODXHQFPBG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- ZBQUMMFUJLOTQC-UHFFFAOYSA-N dichloronickel;3-diphenylphosphaniumylpropyl(diphenyl)phosphanium Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1[PH+](C=1C=CC=CC=1)CCC[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-N 0.000 description 1
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- 229920002457 flexible plastic Polymers 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- BDVZHDCXCXJPSO-UHFFFAOYSA-N indium(3+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[In+3] BDVZHDCXCXJPSO-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- IOOQQIVFCFWSIU-UHFFFAOYSA-M magnesium;octane;bromide Chemical compound [Mg+2].[Br-].CCCCCCC[CH2-] IOOQQIVFCFWSIU-UHFFFAOYSA-M 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/464—Lateral top-gate IGFETs comprising only a single gate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Thin Film Transistor (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は一般的に、有機超小形電子デバイスに関し、より詳細には、実施の形態において、薄膜トランジスタの活物質としてのポリチオフェン類の使用に関する。
【０００２】
【従来の技術】
薄膜トランジスタ（ＴＦＴ）の活性半導体材料として有用な、ある種のポリチオフェン類などの半導体ポリマーが報告されている。これらのポリマーの多くは有機溶媒に適度に良好な溶解度を持つため、例えば、スピンコーティング、溶液キャスティング、浸漬塗布、スクリーン印刷、スタンプ印刷、ジェット印刷等の溶液処理によってＴＦＴ内の半導体チャネル層に加工することができる。通常の溶液処理によって加工できることは、水素化アモルファスシリコンＴＦＴなどのシリコンベースのデバイスに特有のコストの高い従来のフォトリソグラフ処理に比べ、その製造をより簡単かつ低コストにする。更に、ポリマーＴＦＴと呼ばれる、優れた機械的耐久性と構造可撓性とを備えた、ポリチオフェン類などのポリマー材料から作られたトランジスタが望まれている。プラスチック基板上の可撓性ＴＦＴの製造のためには、優れた機械的耐久性と構造可撓性が非常に望ましい。可撓性ＴＦＴは、構造可撓性と機械的耐久性の特性を通常必要とする電子的デバイスの設計を可能にすると考えられる。有機又はポリマートランジスタ要素と共にプラスチック基板を用いれば、従来の堅牢なシリコンＴＦＴを、機械的により頑丈で、構造可撓性のポリマーＴＦＴ設計に代えることができる。後者は、大面積画像センサ、電子ペーパー、その他可撓性ＴＦＴとしての表示媒体などの大面積デバイスを、小型で構造可撓性の設計とすることが可能になる点で特に興味深い。また、スマートカードや無線周波データキャリア（ＲＦＩＤ）タグなどの低価格のマイクロエレクトロニクス用集積回路論理素子や、メモリ／記憶デバイスにポリマーＴＦＴを用いると、その機械的耐久性が著しく向上し、その使用可能寿命が長くなる。
【０００３】
【特許文献１】
米国特許６，１５０，１９１号
【特許文献２】
米国特許６，１０７，１１７号
【特許文献３】
米国特許５，９６９，３７６号
【特許文献４】
米国特許５，６１９，３５７号
【特許文献５】
米国特許５，７７７，０７０号
【０００４】
【発明が解決しようとする課題】
しかし、半導体ポリチオフェン類の多くは、周囲の酸素によって酸化的にドープされ、導電率が増大するため、空気に触れると安定ではない。この結果、これらの材料から製造したデバイスではオフ電流が大きくなり、このため電流オン／オフ比が小さくなってしまう。従ってこれらの材料の多くは、材料加工とデバイス製造の際には環境酸素を排除して酸化的ドーピングを防止するよう厳重な対策を講じなければならない。この予防策は製造コストを押し上げるため、特に大面積デバイスのための、アモルファスシリコン技術に代わる経済的な技術としてのある種のポリマーＴＦＴの魅力が削がれてしまう。これら及びその他の欠点は、本発明の実施の形態において回避され、あるいは最小となる。
【０００５】
本発明は、上記課題を鑑みてなされたものであり、薄膜トランジスタデバイスのような超小形電子デバイスの用途に有用な、ポリチオフェン類などの半導体ポリマーの提供を目的とする。
【０００６】
【課題を解決するための手段】
本発明の参考態様は次のとおりである。下記化２の構造式（Ｉ）を持つポリチオフェンを含む電子的デバイス。
【０００７】
【化２】
式中、Ｒ及びＲ’は側鎖であり、Ａは二価結合基であり、ｘ及びｙは非置換チエニレン単位の数を示し、ｚは０又は１であり、ｘとｙとの和は０より大きく、ｍはセグメントの数を示し、ｎは重合度を示す。;Ｒ及びＲ’はそれぞれ独立して、アルキル及び置換アルキルより選ばれ、Ａはアリーレンである電子的デバイス。；Ｒ及びＲ’は約３〜約２０の炭素原子を含むデバイス。；Ｒ及びＲ’はそれぞれ独立して、アルキルとアルキル誘導体とから成る群より選ばれるものであって、アルキル誘導体は、アルコキシアルキル、シロキシ置換アルキル、パーフルオロアルキルであるパーハロアルキル、及びポリエーテルであり、Ａは、フェニレン、ビフェニレン、フェナントレニレン、ジヒドロフェナントレニレン、フルオレニレン、オリゴアリーレン、メチレン、ポリメチレン、ジアルキルメチレン、ジオキシアルキレン、ジオキシアリーレン、及びオリゴエチレンオキシドである、アリーレンから成る群より選ばれる電子的デバイス。；Ｒ及びＲ’はそれぞれ独立してプロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、及びそれらの異性体から成る群より選ばれるデバイス。；Ａは、炭素数約６〜約４０のアリーレンであるデバイス。；Ｒ及びＲ’は、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、及びペンタデシルから成る群より選ばれ、Ａは、フェニレン、ビフェニレン、及びフルオレニレンから成る群より選ばれ、ｘ及びｙはそれぞれ独立して０〜約１０の数であり、ｍは１〜約５の数であるデバイス。；ｎは約７〜約５，０００であり、いずれもポリスチレン標準を用いたゲル浸透クロマトグラフ法より求めた、ポリチオフェンの数平均分子量（Ｍｎ）は約２，０００〜約１０万であり、重量平均分子量（Ｍｗ）は約４，０００〜約５０万である電子的デバイス。；基板と、ゲート電極と、ゲート誘電体層と、ソース電極及びドレイン電極と、ソース及びドレイン電極とゲート誘電体層とに接した半導体層と、を含み、半導体層はポリチオフェンを含む薄膜トランジスタ。；Ｒ及びＲ’はそれぞれ独立して、アルキル、アルコキシアルキル、シロキシ置換アルキル、及びパーハロアルキルから成る群より選ばれ、Ａは、フェニレン、ビフェニレン、フェナントレニレン、ジヒドロフェナントレニレン、フルオレニレン、オリゴアリーレン、メチレン、ポリメチレン、ジアルキルメチレン、ジオキシアルキレン、ジオキシアリーレン、及びオリゴエチレンオキシドから成る群より選ばれる薄膜トランジスタデバイス。；ｎは約５〜約５，０００であり、いずれもポリスチレン標準を用いたゲル浸透クロマトグラフ法より求めた、ポリチオフェンの数平均分子量（Ｍｎ）は約４，０００〜約５万であり、重量平均分子量（Ｍｗ）は約５，０００〜約１０万である薄膜トランジスタデバイス。；Ｒ及びＲ’は約３〜約２０の炭素原子を含むアルキルである薄膜トランジスタデバイス。；Ａは炭素数約６〜約３０のアリーレンである薄膜トランジスタデバイス。；Ａは炭素数約６〜約２４のアリーレンである薄膜トランジスタデバイス。；Ａは、フェニレン、ビフェニレン、又はフルオレニレンである薄膜トランジスタデバイス。；保護層を備えた薄膜トランジスタデバイス。；下記化３に記載の構造式（２）で表されるポリチオフェンを含み、式中、ｎは重合度であって、５から５０００である薄膜トランジスタ。
【０００８】
【化３】
【化４】
【化５】
；ｎは約５〜約５，０００であるデバイス。；ｎは約１０〜約１，０００であるデバイス。；Ｍｎは約４，０００〜約５万、Ｍｗは約５，０００〜約１０万であるデバイス。；参考態様のポリチオフェンは、下記化６，７に記載の構造式（１）〜（８）を持つポリチオフェン類から成る群より選ばれるデバイス。
【０００９】
【化６】
【化７】
；参考態様のポリチオフェンは、下記化８から化１１に記載の構造式（１）〜（１４）を持つポリチオフェン類から成る群より選ばれる薄膜トランジスタデバイス。
【００１０】
【化８】
【化９】
【化１０】
【化１１】
；参考態様のポリチオフェンは、下記化１２，１３に記載の構造式（１）〜（８）を持ち、必要に応じて、式中、ｎは約５〜約５，０００であるポリチオフェン類から成る群より選ばれる薄膜トランジスタデバイス。
【００１１】
【化１２】
【化１３】
；ｘ、ｙ、及びｍは１〜３であり、ｚは０又は１であり、デバイスは薄膜トランジスタであるデバイス。；ｘ、ｙ、及びｍは１であり、ｚは０又は１であり、デバイスは薄膜トランジスタであるデバイス。；ｘ、ｙ、及びｍは１であり、ｚは０又は１であり、あるいは、ｘ、ｙ、及びｍは１であり、ｚは０であり、デバイスは薄膜トランジスタであるデバイス。；基板は、ポリエステル、ポリカーボネート、又はポリイミドであるプラスチックシートであり、ゲート、ソース、及びドレイン電極は、金、ニッケル、アルミニウム、プラチナ、酸化インジウムチタン、又は導電性ポリマーを含み、ゲート誘電体層は、窒化ケイ素、酸化ケイ素、又は絶縁性ポリマーを含むものである薄膜トランジスタデバイス。；基板は、ガラス又はプラスチックシートであり、ゲート、ソース、及びドレイン電極はそれぞれ金を含み、ゲート誘電体層は、ポリ（メタクリレート）、ポリ（ビニルフェノール）である有機ポリマーを含むものである薄膜トランジスタデバイス。；ゲート、ソース、及びドレイン電極は、ポリスチレンスルホナートをドープしたポリ（３，４−エチレンジオキシチオフェン）であるドープした有機導電性ポリマー、あるいは、ポリマーバインダ中にコロイド状に分散した銀を含む導電性インキ／ペーストから製造され、ゲート誘電体層は、有機ポリマー又は無機酸化物粒子−ポリマー複合材である薄膜トランジスタデバイス。；下記化１４に包含されるポリチオフェン類。
【００１２】
【化１４】
式中、Ｒ及びＲ’は側鎖であって、それぞれ独立して例えば、アルキル及びアルキル誘導体から成る群より選ばれ、アルキル誘導体は、アルコキシアルキル、シロキシ置換アルキル、パーフルオロアルキルなどのパーハロアルキル、オリゴエチレンオキシドなどのポリエーテル、ポリシロキシ、等であり、Ａは二価結合基であって、例えば、フェニレン、ビフェニレン、フェナントレニレン、ジヒドロフェナントレニレン、フルオレニレン、オリゴアリーレン、メチレン、ポリメチレン、ジアルキルメチレン、ジオキシアルキレン、ジオキシアリーレン、及びオリゴエチレンオキシド、等のアリーレンから成る群より選ばれ、ｘ及びｙはそれぞれ独立して０〜１０より選ばれる整数であり、ｚは０又は１のいずれかであり、ｘとｙとの和は０より大きく、ｍは１〜約５の整数であり、ｎは重合度であって、通常、約５〜５，０００以上、より詳細には約１０〜約１，０００とすることができる。いずれもポリスチレン標準を用いたゲル浸透クロマトグラフ法より求めた、ポリチオフェン類の数平均分子量（Ｍｎ）は、例えば約２，０００〜約１０万、より詳細には約４，０００〜約５万とすることができ、その重量平均分子量（Ｍｗ）は約４，０００〜約５０万、より詳細には約５，０００〜約１０万とすることができる。
【００１３】
側鎖Ｒ及びＲ’の例としては、例えば炭素数約１〜約２５、より詳細には約４〜約１２の、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、それらの異性体、等のアルキル、炭素数１〜約２５の、例えば、メトキシプロピル、メトキシブチル、メトキシヘキシル、メトキシヘプチル、等のアルコキシアルキル、ポリエチレンオキシドなどのポリエーテル鎖、パーフルオロアルキル（例えば、ノナフルオロヘキシル、ノナフルオロヘプチル、ペンタデカフルオロオクチル、トリデカフルオロノニル、等）などのパーハロアルキル、トリアルキルシロキシアルキル等のポリシロキシ鎖などが挙げられる。
【００１４】
使用されるポリチオフェン類は、繰り返しチエニレン単位を含むことができ、その中では特定のチエニレンだけが側鎖を持ち、またチエニレン単位はポリチオフェン主鎖上に位置規則性（レジオレギュラ：regioregular）に配列している。
【００１５】
このポリチオフェン類は実施の形態において実質的に安定であり、周囲条件でこれを用いたデバイスの製造が可能である。またそのデバイスは高い電流オン／オフ比を持ち、更に操作上より安定で、その性能は通常、位置規則性ポリ（３−アルキルチオフェン−２，５−ジイル）などの公知の位置規則性ポリチオフェン類から製造したもののように急激に低下することがない。より詳細には、本発明のポリチオフェン類は実施の形態において、非置換の２,５−チエニレン単位と、必要に応じて二価結合基とに挾まれた、３，４−二置換−２，５−チエニレン単位の繰り返しセグメントを含む。側鎖は、薄膜製造の際にポリチオフェン類の分子自己組織化の誘発及び促進を促す。多少の回転自由度を持つ非置換チエニレン単位と必要に応じた二価結合基は、ポリチオフェン鎖に沿って伸びるπ共役を妨げ、その酸化的ドーピング傾向を抑制することができる。
【００１６】
本発明は、上記特徴により、薄膜トランジスタデバイスのような超小形電子デバイスの用途に有用な、ポリチオフェン類などの半導体ポリマーの提供することができる。
【００１７】
また、本発明は、その薄膜の吸収スペクトルから求めたバンドギャップが約１．５〜約３ｅＶであるポリチオフェン類の提供であり、このポリチオフェン類は、薄膜トランジスタ半導体チャネル層材料としての使用に適する。
【００１８】
更に本発明は、超小形電子部品として有用なポリチオフェン類の提供であり、このポリチオフェン類は、ジクロロメタン、テトラヒドロフラン、トルエン、キシレン、メシチレン、クロロベンゼン等の一般的な有機溶媒に適度な、例えば約０.１重量％以上の溶解度を持ち、このためスピンコーティング、スクリーン印刷、スタンプ印刷、浸漬塗布、溶液キャスティング、ジェット印刷等の溶液処理によって経済的に加工することができる。
【００１９】
別の本発明の特徴は、ポリチオフェンチャネル層を持ち、その層の導電率が１０-6〜約１０-9Ｓ／ｃｍ（ジーメンス／センチメートル）である薄膜トランジスタなどの電子的デバイスの提供である。
【００２０】
また更に本発明の特徴は、ポリチオフェン類とそれを用いたデバイスの提供であり、このデバイスは酸素の悪影響に対して優れた抵抗性を示し、つまりこのデバイスは比較的高い電流オン／オフ比を示し、その性能は通常、位置規則性ポリ（３−アルキルチオフェン−２,５−ジイル）などの位置規則性ポリチオフェン類から製造したもののように急激に低下することなく、あるいは最小限の低下と同程度である。
【００２１】
また別の本発明の特徴は、特殊な構造的特徴を持ち、これにより適当な加工条件下において分子が自己配列し、またその構造的特徴がデバイス性能の安定性をも向上させるようなポリチオフェン類の提供である。適当な分子配列は、薄膜中により高次の分子構造配列を形成し、効率良く電荷キャリアを移動させて高い電気的性能を可能とする。
【００２２】
【発明の実施の形態】
本実施の形態における薄膜トランジスタは、下記化１５に記載の構造式（２）で表されるポリチオフェンを含み、式中、ｎは重合度であって、５から５０００であることを特徴とする。ポリチオフェン類の例を下記化１５から化１８に示す。
【００２３】
【化１５】
【化１６】
【化１７】
【化１８】
構造式（Ｉ）を参照するならば、ポリチオフェン類は、３，４−二置換−２，５−チエニレン単位と、非置換２，５−チエニレン単位と、必要に応じて二価の結合基との位置規則性セグメントを含むものである。ポリチオフェン（Ｉ）（構造式（１）〜（１４）を参照）中の側鎖の位置規則性は、適当な加工条件下で薄膜を製造する際に分子の自己配列を誘導し、薄膜中に高度に組織化された微細構造を作ることができると考えられる。薄膜トランジスタの半導体チャネル層中の高次の微細構造はトランジスタ性能を向上する。これらのポリチオフェン類は、適当な溶媒系に溶解した溶液から厚さ約１０〜約５００ｎｍの薄膜を作ると、強い分子内π−πスタックが形成され、導電性となって効率良く電荷キャリヤを移動すると考えられる。（Ｉ）中の非置換チエニレン部分は多少の回転自由度を持つため、酸化的ドーピングを十分に抑制する程度に（Ｉ）の分子内に広がるπ共役を妨げる。従って、このポリチオフェン類は周囲条件下で安定であり、これらのポリチオフェン類から製造したデバイスは、位置規則性ポリ（３−アルキルチオフェン−２，５−ジイル）などの位置規則性ポリチオフェン類より機能的により安定である。保護しなくても、構造式（Ｉ）のポリチオフェン類から製造したデバイスは、その実施の形態において、通常数週間から数ヶ月間、例えば約３〜約１２週間も安定である。これに対し、位置規則性ポリ（３−アルキルチオフェン−２，５−ジイル）を用いたデバイスは、周囲の酸素に曝すと数日で、例えば５日足らずで劣化してしまう。本願のポリチオフェン類から製造したデバイスはまた、高い電流オン／オフ比を持ち、その性能は、材料調製、デバイス製造、及び評価の際に周囲の酸素を排除するよう厳しい操作上の予防措置を講じなくても、ポリ（３−アルキルチオフェン−２，５−ジイル）のものほど急激には変化しない。酸化的ドーピングに対して安定な材料は、低コストデバイスの製造には特に有用である。この材料はより安定であるため、通常、厳重に不活性な雰囲気中で取り扱う必要がなく、故にその製造工程がより単純かつ低コストで、その工程をシンプルな大規模製造工程とすることができる。
【００２４】
実施の形態においてこのポリチオフェン類は、一般的な被覆用溶媒に可溶であり、例えば、ジクロロメタン、１，２−ジクロロエタン、テトラヒドロフラン、トルエン、キシレン、メシチレン、クロロベンゼン等の溶媒に約０．１重量％以上、より詳細には約０．５〜約１５重量％の溶解度を持つ。更に、このポリチオフェン類を薄膜トランジスタデバイスの半導体チャネル層に加工すると安定した導電率となり、例えば、一般的な４プローブ伝導率測定法によれば、約１０-9〜約１０-6Ｓ／ｃｍ、より詳細には約１０-8〜約１０-7Ｓ／ｃｍである。
【００２５】
本発明のポリチオフェン類は、適切に組み立てられたモノマー、例えば、トリチオフェンモノマーの重合により調製可能である。例えば、スキーム１に従って例示のポリチオフェン類（Ia）及び（Ib）を調製するには、２，５−ビス（２−チエニル）−３，４−ジ−Ｒ−チオフェン（IIａ）、又は２，５−ビス（５−ブロモ−２−チエニル）−３，４−ジ−Ｒ−チオフェン（IIb）を用いる。モノマー類（IIa）及び（IIb）はそれぞれその中央のチエニレン単位上に２つの側鎖を持つため、重合すると側鎖がそれぞれのポリチオフェン主鎖上に位置規則性に並んだポリチオフェン類(Ia)及び(Ib)となる。位置規則性カップリング反応が必要なポリ（３−アルキルチオフェン−２，５−ジイル）などの位置規則性ポリチオフェン類の調製とは異なり、本発明のポリチオフェン類は、位置規則性の複雑さの無い通常の重合法により調製できる。詳細には、（Ia）は、ＦｅＣｌ3を介在させた酸化的カップリング重合によりモノマー (IIa)から、あるいはレイケ（Reike）亜鉛で処理後Ｎｉ（ｄｐｐｅ）Ｃｌ2触媒を加えることによりモノマー(IIb)から調製できる。一方、ポリチオフェン（Ib)は、適当なアリーレンジボロナートとのスズキカップリング反応により(IIb)から容易に得ることができる。
【００２６】
【化１９】
詳細には、（IIa）の重合は、乾燥空気の気流中で、塩化物溶媒、例えばクロロホルムに溶解した（IIa）の１モル当量の溶液を、約１〜約５モル当量の無水ＦｅＣｌ３のクロロホルム懸濁液に加えることにより行うことができる。得られた混合物を、乾燥空気気流中、あるいは乾燥空気の泡をゆっくり反応混合物中に通しながら、約２５〜約５０℃の温度で、約３０分〜約４８時間反応させる。反応後、反応混合物を水又は希塩酸水溶液で洗い、希アンモニア水溶液と撹拌した後に水で洗い、次にメタノール又はアセトンから沈殿させてポリマー生成物を単離する。レイケ亜鉛法では、無水テトラヒドロフランに溶解した１０ミリモル当量の（IIｂ）を、１１ミリモル当量の調製直後のレイケＺｎの無水テトラヒドロフラン懸濁液に、２０〜４０分かけて良く撹拌しながら滴下して加え、次に得られた混合物を、室温（約２２〜約２５℃）で約３０分〜約２時間反応させる。続いて、約０．１ミリモル当量のＮｉ（ｄｐｐｅ）Ｃｌ２の無水テトラヒドロフラン懸濁液を約１０〜約２０分かけてゆっくり加え、次に混合物を約４０〜約６５℃で２〜５時間加熱する。次に反応混合物を、激しくかき混ぜながら希塩酸−メタノール溶液に注ぎ、ポリマー生成物を沈殿させる。後者を熱テトラヒドロフランに再溶解した後、希アンモニア−メタノール溶液から再沈殿させる。
【００２７】
より詳細には、ポリチオフェン（Ib）は、モノマー（IIb）と適当なアリーレンジボロナートとのスズキカップリング反応より得られる。等モル当量のモノマー（IIb）とアリーレンジボロナートとのトルエン溶液と、約２〜６モル％のテトラキス（トリフェニルホスフィン）パラジウムと、１〜２Ｍの水溶液とした約２〜約４モル等量の炭酸ナトリウムなどの無機塩基と、約１〜５モル％の、テトラブチルアンモニウム＝クロリド又はトリカプリリルメチルアンモニウム＝クロリドなどの相間移動触媒との混合物を、不活性雰囲気中で４８時間、約９０℃に加熱する。重合後、ポリチオフェン生成物（Ib）をメタノールから繰り返し沈殿させて単離する。
【００２８】
本発明の様々な代表的な実施の形態を図１〜図４に示す。ここでは薄膜トランジスタ（ＴＦＴ）構造体中のチャネル材料としてポリチオフェン類を用いている。
【００２９】
図１は、基板１６と、それに接した金属接点１８（ゲート電極）と、絶縁性誘電体層１４の層と、その上又はその頂部に置かれた２つの金属接点２０及び２２（ソース及びドレイン電極）とを含む薄膜トランジスタ構造体１０の概略図である。金属接点２０及び２２の上と間にはポリチオフェン半導体層１２がある。
【００３０】
図２は、基板３６と、ゲート電極３８と、ソース電極４０と、ドレイン電極４２と、絶縁性誘電体層３４と、ポリチオフェン半導体層３２とを含む、別の薄膜トランジスタ構造体３０の概略図である。
【００３１】
図３は、ゲート電極として作用する高濃度ｎ−ドープシリコンウエハ５６と、熱により生成した酸化ケイ素誘電体層５４と、ポリチオフェン半導体層５２と、その上に置かれたソース電極６０とドレイン電極６２とを含む薄膜トランジスタ構造体５０の概略図である。
【００３２】
図４は、基板７６と、ゲート電極７８と、ソース電極８０と、ドレイン電極８２と、ポリチオフェン半導体層７２と、絶縁性誘電体層７４とを含む、別の薄膜トランジスタ構造体７０の概略図である。
【００３３】
本発明の一部の実施の形態では、必要に応じて、図１〜図４の各トランジスタ構造体の上に保護層を加えても良い。図４の薄膜トランジスタ構造体では、絶縁性誘電体層７４は保護層として機能することもできる。
【００３４】
基板層は一般に、目的とする用途に応じて、様々な適当な形のシリコンを含むシリコン材料、ガラス板、プラスチックフィルム又はシート、等である。構造可撓性のデバイスでは、例えば、ポリエステル、ポリカーボネート、ポリイミドシート等のプラスチック基板が望ましい。基板の厚さは、約１０μｍ〜１０ｍｍ以上であり、詳細な厚さは、特に可撓性のプラスチック基板では約５０〜約１００μｍ、ガラス又はシリコンなどの堅牢な基板では約１〜約１０ｍｍである。
【００３５】
ゲート電極をソース及びドレイン電極と隔て、半導体層に接している絶縁性誘電体層は一般に、無機材料膜、有機ポリマー膜、又は有機−無機複合材膜とすることができる。誘電体層の厚さは、例えば約１０ｎｍ〜約１μｍ、より詳細な厚さは約１００〜約５００ｎｍである。誘電体層に適した無機材料の具体例としては、酸化ケイ素、窒化ケイ素、酸化アルミニウム、チタン酸バリウム、ジルコン酸チタン酸バリウム、等が挙げられ、誘電体層に適した有機ポリマーの具体例としては、ポリエステル類、ポリカーボネート類、ポリ（ビニルフェノール）、ポリイミド類、ポリスチレン、ポリ（メタクリレート）類、ポリ（アクリレート）類、エポキシ樹脂、等が挙げられ、無機−有機複合材料の具体例としては、ポリエステル、ポリイミド、エポキシ樹脂等のポリマー中に分散した超微小金属酸化物粒子などが挙げられる。絶縁性誘電体層の厚さは通常、使用する誘電体材料の比誘電率に応じて約５０〜約５００ｎｍである。より詳細には、誘電体材料は約３以上の比誘電率を持つため、約３００ｎｍの適当な誘電体の厚さがあれば望ましい静電容量、例えば約１０-9〜約１０-7Ｆ／ｃｍ2とすることができる。
【００３６】
誘電体層とソース／ドレイン電極との間に接して、本願に述べるポリチオフェン類を含む活性半導体層を置く。この層の厚さは通常約１０ｎｍ〜約１μｍ、又は約４０〜約１００ｎｍである。この層は通常、スピンコーティング、キャスティング、スクリーン、スタンプ、又はジェット印刷などの溶液処理によって本発明のポリチオフェン類の溶液から製造可能である。
【００３７】
ゲート電極は、金属薄膜、導電性ポリマー膜、導電性インキ又はペーストから作った導電性膜、あるいは基板自体（例えば、高濃度にドープしたシリコン）とすることができる。ゲート電極材料の例としては、アルミニウム、金、クロム、酸化インジウムスズ、導電性ポリマー類、導電性インキ／ペースト等が挙げられるが、これらに限るものではない。導電性ポリマーは、ポリスチレンスルホナートをドープしたポリ（３，４−エチレンジオキシチオフェン）（ＰＳＳ−／ＰＥＤＯＴ）などであり、導電性インキ／ペーストは、カーボンブラック／グラファイト又はコロイド状の銀をポリマーバインダ中に分散したもの（例えば、アチソン・コロイズ社（Acheson Colloids Company）製のエレクトロダグ（ELECTRODAG））や、銀を充填した導電性熱可塑性インキ（ノエル・インダストリーズ（Noelle Industries）製）である。ゲート層は、真空蒸着、金属や導電性金属酸化物のスパッタリング、導電性ポリマー溶液又は導電性インキのスピンコーティング、キャスティング、又は印刷による塗布によって調製できる。ゲート電極層の厚さは約１０ｎｍ〜約１０μｍの範囲であり、金属薄膜に望ましい厚さは約１０〜約２００ｎｍの範囲であり、ポリマー導電体では約１〜約１０μｍの範囲である。
【００３８】
ソース及びドレイン電極層は、半導体層に対して低抵抗オーム接触となる材料から製造することができる。ソース及びドレイン電極としての使用に適した典型的な材料は、金、ニッケル、アルミニウム、プラチナ、導電性ポリマー、導電性インキなどのゲート電極材料として挙げられたものなどである。この層の典型的な厚さは、例えば約４０ｎｍ〜約１μｍであり、より詳細な厚さは約１００〜約４００ｎｍである。ＴＦＴデバイス構造体は、幅Ｗ、長さＬの半導体チャネルから成る。半導体チャネル幅は約１０μｍ〜約５ｍｍであり、望ましいチャネル幅は約１００μｍ〜約１ｍｍである。半導体チャネル長さは約１μｍ〜約１ｍｍであり、より詳細なチャネル長さは約５〜約１００μｍである。
【００３９】
ソース電極は接地しており、通常約＋１０〜約−８０ボルトの電圧をゲート電極に印加したときに、半導体チャネルを通って移動する電荷キャリヤを集めるため、通常約０〜約−８０ボルトのバイアス電圧をドレイン電極に印加する。
【００４０】
【実施例】
ａ）デバイスの製造：
基本的な供試デバイス配置として、図１及び図３にそれぞれ図示したボトムコンタクト型及びトップコンタクト型薄膜トランジスタ構造体を用いた。ボトムコンタクト型供試デバイスは、ガラス基板上に写真平板で予めパターンを形成した一連のトランジスタの誘電体層と、規定のチャネル幅と長さの電極とを含むものである。ガラス基板上のゲート電極は厚さ約８０ｎｍのクロムから成るものであった。ゲート誘電体は、約２２ｎＦ／ｃｍ2（ナノファラッド／平方センチメートル）の静電容量を持つ、厚さ３００ｎｍの窒化ケイ素であった。ゲート誘電体層の頂部又はその上に被覆して、厚さ約１００ｎｍの金から成るソース及びドレイン接点を真空蒸着した。次に、厚さ約３０〜約１００ｎｍの供試ポリチオフェン半導体層を、周囲の酸素、湿気、又は光への暴露を防止する対策を何ら講じることなく、周囲条件下でスピンコーティングにより塗布した。半導体層の製造に用いた溶液は、適当な溶媒に溶解した１重量％のポリチオフェンから成るものであり、使用前に０．４５μｍのフィルタで濾過した。スピンコーティングは、回転速度１，０００ｒｐｍで約３５秒間行った。得られた被覆デバイスは、真空中８０℃で２０時間乾燥した後、評価に供した。
【００４１】
トップコンタクト型供試デバイスは、ｎ−ドープシリコンウエハと、その上に熱生成させた厚さ約１１０ｎｍの酸化ケイ素層とを含む。ウエハがゲート電極として機能する一方、酸化ケイ素層はゲート誘電体として働き、その静電容量は約３２ｎＦ／ｃｍ2であった。シリコンウエハをまずメタノールで清浄にし、空気乾燥後、０．０１Ｍの１，１，１，３，３，３−ヘキサメチルジシラザンのジクロロメタン溶液に、室温（２２〜２５℃）で３０分間浸した。次にこのウエハをジクロロメタンで洗い、乾燥した。スピンコーティングにより、厚さ約３０〜約１００ｎｍの半導体ポリチオフェン層を酸化ケイ素誘電体層の上に塗布し、真空中８０℃で２０時間乾燥した。デバイス製造の際、周囲の酸素、湿気、又は光への材料の暴露を防止する対策は講じなかった。次に、金のソース及びドレイン電極を、半導体ポリチオフェン層の上に、様々なチャネル長さと幅のシャドウマスクを通して真空蒸着し、様々な大きさの一連のトランジスタを製作した。念のため製造後のデバイスは、評価の前後には相対湿度約３０％の乾燥雰囲気中、暗所で保存した。
【００４２】
ｂ）ＴＦＴデバイスの特性評価：
電界効果トランジスタの性能を、キースリー（Keithley）４２００ＳＣＳ半導体特性評価デバイスを用いて、暗箱中周囲条件で評価した。キャリヤ移動度（μ）は、飽和領域（ゲート電圧、ＶG＜ソース−ドレイン電圧、ＶSD）におけるデータより、下記の式（１）に従って計算した。
【００４３】
【式１】
ＩSD＝Ｃiμ（Ｗ／２Ｌ）（ＶG−ＶT）2 （１）
式中、ＩSDは飽和領域におけるドレイン電流であり、ＷとＬはそれぞれ半導体チャネルの幅と長さであり、Ｃiはゲート誘電体層の単位面積当たりの静電容量であり、ＶG及びＶTはそれぞれ、ゲート電圧及びしきい電圧である。このデバイスのＶTは、飽和領域におけるＩSDの平方根と、測定データからＩSD＝０を外挿して求めたデバイスのＶGとの関係から求めた。
【００４４】
薄膜トランジスタの特性を表す値は、その電流オン／オフ比である。これはゲート電圧ＶGがドレイン電圧ＶDと等しいかそれ以上であるときの飽和ソース−ドレイン電流と、ゲート電圧ＶGがゼロの時のソース−ドレイン電流との比である。
【００４５】
比較例
公知の位置規則性ポリチオフェン、ポリ（３−ヘキシルチオフェン−２，５−ジイル）を用いる以外は本質的に前記の手順を繰り返して、図１及び図３にそれぞれ示したボトムコンタクト型デバイス及びトップコンタクト型デバイスを製作した。この材料はアルドリッチ・ケミカル（Aldrich Chemical）より購入し、そのクロロベンゼン溶液からメタノールへの沈殿を３回繰り返して精製した。
【００４６】
半導体ポリチオフェン層は、前述の手法に従い、１重量％の位置規則性ポリ（３−ヘキシルチオフェン−２，５−ジイル）のクロロベンゼン溶液のスピンコーティングにより、周囲条件下でデバイス上に被覆した。このデバイスは、評価前に真空中８０℃で２０時間乾燥した。各デバイスに対し５個以上のトランジスタから得た平均特性値を次にまとめた。
（１） ボトムコンタクト型デバイス（Ｗ＝１，０００μｍ，Ｌ＝１０μｍ）
移動度：１〜２．３×１０-3ｃｍ2／Ｖ．ｓｅｃ
初期電流オン／オフ比：０．８〜１×１０3
５日後の電流オン／オフ比：５〜１０
（２） トップコンタクト型デバイス（Ｗ＝５，０００μｍ，Ｌ＝６０μｍ）
移動度：１〜１．２×１０-2ｃｍ2／Ｖ．ｓｅｃ
初期電流オン／オフ比：１．５〜２．１×１０3
５日後の電流オン／オフ比：５〜１０
【００４７】
観察された初期電流オン／オフ比が低いのは、ポリ（３−ヘキシルチオフェン−２，５−ジイル）が酸化的ドーピングを受け易く、すなわち環境酸素の存在下ではポリ（３−ヘキシルチオフェン−２，５−ジイル）が不安定であることを示している。僅か５日間のうちに電流オン／オフ比が著しく減少するのも、周囲条件でのポリ（３−ヘキシルチオフェン−２，５−ジイル）の甚だしい機能不安定性を更に裏付けている。
【００４８】
実施例
（ａ）ポリ［２，５−ビス（２−チエニル）−３，４−ジオクチルチオフェン］（２）の合成
ｉ）モノマーの合成：ポリチオフェン（２）の調製に用いるモノマー、２，５−ビス（５−ブロモ−２−チエニル）−３，４−ジオクチルチオフェンを次のように合成した。
【００４９】
３，４−ジオクチルチオフェン：不活性雰囲気中、氷浴で冷却した５００ｍｌの丸底フラスコ中で、２００ｍｌの無水ジエチルエーテルに溶解したジクロロ［１，３−ビス（ジフェニルホスフィノ）プロパン］ニッケル（II）（０．２ｇ）と、３，４−ジブロモチオフェン（２０．１６ｇ、０．０８３３ｍｏｌ）との混合物を良くかき混ぜながら、これに２Ｍのオクチルマグネシウム＝ブロミド（１００ｍｌ、０．２ｍｏｌ）の無水ジエチルエーテル溶液を加えた。ニッケル錯体はすぐにグリニャール試薬と反応し、得られた反応混合物を室温まで暖まるに任せた。発熱反応は３０分以内に始まり、ジエチルエーテルが穏やかに還流し始めた。更に２時間室温で撹拌後、反応混合物を６時間還流し、氷浴で冷やし、２Ｎの塩酸水溶液で加水分解した。有機層を分け、水で、次に塩水で洗い、再び水で洗った後、無水硫酸ナトリウムに通して乾燥させた。溶媒を蒸発後、残留物をクーゲルロア（Kugelrohr）デバイスに通して減圧下で蒸留し、無色液体として２１．３ｇの３，４−ジオクチルチオフェンを得た。
1Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ６．８９（ｓ，２Ｈ），２．５０（ｔ，Ｊ＝７．０Ｈｚ，４Ｈ），１．６４−１．５８（ｍ，４Ｈ）， １．４０−１．２８（ｍ，２０Ｈ），０．８９（ｔ， Ｊ＝６．５Ｈｚ，６Ｈ）
13Ｃ−ＮＭＲ（ＣＤＣｌ3）：δ１４２．１，１１９．８，３１．９，２９．６（２Ｃ），２９．５，２９．３，２８．８，２２．７，１４．１
【００５０】
２，５−ジブロモ−３，４−ジオクチルチオフェン：１００ｍｌの丸底フラスコ中で、３０ｍｌのジクロロメタンと１０ｍｌの酢酸との混合物に溶解した３，４−ジオクチルチオフェン（３．６ｇ、１１．７ｍｍｏｌ）の溶液を良く撹拌しながら、これにＮ−ブロモスクシンイミド（４．６ｇ、２５．７ｍｍｏｌ）を加えた。薄層クロマトグラフ法により反応の様子を観察したところ、約３５分で完了した。この混合物を１６０ｍｌのジクロロメタンで希釈し、濾過してスクシンイミドを除いた。濾液を２Ｎの水酸化ナトリウム水溶液で洗い、次に水で２回洗った（２×１００ｍｌ）。無水硫酸ナトリウムで乾燥後溶媒を除き、淡黄色の液体として５．４ｇの２，５−ジブロモ−３，４−ジオクチルチオフェンを得た。
1Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ２．５０（ｔ，Ｊ＝７．０Ｈｚ，４Ｈ），１．５２−１．２８（ｍ，２４Ｈ），０．８９（ｔ，Ｊ＝６．５Ｈｚ，６Ｈ）
【００５１】
２，５−ビス（２−チエニル）−３，４−ジオクチルチオフェン：不活性雰囲気中の乾燥箱の中、２５０ｍｌの丸底フラスコ中で、無水テトラヒドロフラン（５０ｍｌ）に溶解した、２，５−ジブロモ−３，４−ジオクチルチオフェン（４．２ｇ、９．０ｍｍｏｌ）と、２−（トリブチルスズ）チオフェン（７．４ｇ、１９．８ｍｍｏｌ）との混合物に、Ｐｄ（ＰＰｈ3）2Ｃｌ2（０．１５ｇ，０．２ｍｍｏｌ）を加えた。次にこの混合物を１２時間還流し、溶媒を留去した。こうして得られた粗生成物を、溶離液としてヘキサンを用いたシリカゲル上でのフラッシュ（flash）クロマトグラフ法により精製し、３．１ｇの２，５−ビス（２−チエニル）−３，４−ジオクチルチオフェンを得た。
1Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ７．３１（ｄｄ，Ｊ＝３．２，０．５Ｈｚ，２ Ｈ），７．１３（ｄｄ，Ｊ＝２．２，０．５Ｈｚ，２Ｈ），７．０６（ｄｄ，Ｊ＝２．２，４．５Ｈｚ， ２Ｈ），２．６８（ｄｄ，Ｊ＝７．６，７．６Ｈｚ， ４Ｈ），１．５９−１．５３（ｍ，４Ｈ），１．４２−１．２７（ｍ，２０Ｈ），０．９１（ｔ，Ｊ＝６．５Ｈｚ，６Ｈ）
【００５２】
２，５−ビス（５−ブロモ−２−チエニル）−３，４−ジオクチルチオフェン：氷浴で冷却した１００ｍｌの丸底フラスコ中で、Ｎ，Ｎ−ジメチルホルムアミド（３０ｍｌ）に溶解した２，５−ビス（２−チエニル）−３，４−ジオクチルチオフェン（３．６ｇ、７．６ｍｍｏｌ）の溶液を良く撹拌しながら、これにＮ−ブロモスクシンイミド（２．８ｇ、１５．７ｍｍｏｌ）を加えた。添加後、混合物がゆっくりと室温まで暖まるに任せた。薄層クロマトグラフ法で反応を観察したところ、３時間後には反応は止まった。得られた混合物をヘキサン（１７０ｍｌ）で希釈し、１００ｍｌの水で３回洗った。有機層を分け、無水硫酸ナトリウムで乾燥し、真空蒸発させて粗生成物を得た。これを、溶離液としてヘキサンを用いたシリカゲル上のフラッシュクロマトグラフ法により精製し、２．５ｇの２，５−ビス（５−ブロモ−２−チエニル）−３，４−ジオクチルチオフェンを得た。
1Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ７．０６（ｄ，Ｊ＝３．５Ｈｚ，２Ｈ），６．８６（ｄ，Ｊ＝３．５Ｈｚ，２Ｈ），２．６２（ｄｄ， Ｊ＝７．３，７．３Ｈｚ，４Ｈ），１．５５−１．４９（ｍ，４Ｈ），１．４１−１．２８（ｍ，２０Ｈ），０．８９（ｔ，Ｊ＝６．５Ｈｚ，６Ｈ）
13Ｃ−ＮＭＲ（ＣＤＣｌ3）；δ１４０．６，１３７．４，１３０．２，１２９． ３，１２６．２，１１２．０，３１．９，３０．８， ２９．８，２９．２（２Ｃ），２８．１，２２．７， １４．２
【００５３】
ポリ［２，５−ビス（２−チエニル）−３，４−ジオクチルチオフェン］（２）：無水テトラヒドロフラン（１０ｍｌ）に溶解した２，５−ビス（５−ブロモ−２−チエニル）−３，４−ジオクチルチオフェン（２．４６ｇ、３．９ｍｍｏｌ）の溶液に、調製直後のレイケＺｎ（０．２８ｇ，４．２９ｍｍｏｌ）を無水テトラヒドロフラン（２０ｍｌ）に懸濁したものを良く撹拌しながら、不活性雰囲気中で滴下して加え、この混合物を４５分間室温で反応させた。次に、無水テトラヒドロフラン（３５ｍｌ）に懸濁させたＮｉ（ｄｐｐｅ）Ｃｌ2（０．０２１ｇ、０．０４ｍｍｏｌ）を注意しながら加えた。反応混合物を６０℃で３時間加熱後、２Ｎの塩酸−メタノール溶液中に注いだ。沈殿したポリチオフェン生成物を濾過し、７０ｍｌの熱テトラヒドロフランに再溶解し、２Ｎのアンモニア−メタノール溶液から沈殿させた。この操作を２度繰り返し、酸とオリゴマーとを除いた。真空中、室温で乾燥後、１．６ｇの、Ｍw４１，９００、Ｍn１１，８００Ｋ、Ｔｍ１８０℃のポリ［２，５−ビス（２−チエニル）−３，４−ジオクチルチオフェン］（２）を得た。
1Ｈ−ＮＭＲ（ＣＤＣｌ3）：δ７．３０，７．１３，７．０５，２．７３，１．５９，１．４５，１．２９，０．８９
13Ｃ−ＮＭＲ（ＣＤＣｌ3）：δ１４０．４，１３６．７，１３５．１，１２９． ８，１２６．４，１２３．９，３１．９，３０．７， ２９．９，２９．３，２８．３，２２．７，１４．２
【００５４】
図１及び図３にそれぞれ図示した、ひとつはボトムコンタクト型もうひとつはトップコンタクト型配置の２つの供試デバイスを、前述の製造手順に従い上記のポリチオフェンを用いて製造した。デバイスは、評価の前に真空中８０℃で２０時間乾燥させた。各デバイスに対し５個以上のトランジスタから得た平均特性値を次にまとめた。
（１）ボトムコンタクト型デバイス（Ｗ＝１，０００μｍ、Ｌ＝１０μｍ）
移動度：３．４×１０-4〜１．３×１０-3ｃｍ2／Ｖ．ｓｅｃ
初期電流オン／オフ比：０．８〜１．３×１０4
５日後の電流オン／オフ比：５．０〜７．０×１０3
（２）トップコンタクト型デバイス（Ｗ＝５，０００μｍ、Ｌ＝６０μｍ）
移動度：１．３〜３．１×１０-3ｃｍ2／Ｖ．ｓｅｃ
初期電流オン／オフ比：１．５〜２．６×１０5
５日後の電流オン／オフ比：１．１〜２．０×１０5
３０日後の電流オン／オフ比：８．０〜９．５×１０4
【００５５】
初期電流オン／オフ比が大きく、時間を経ても電流オン／オフ比の低下が遅いことから、本発明の実施の形態のポリチオフェン半導体層が安定であることが示された。
【図面の簡単な説明】
【図１】 本発明によるポリチオフェン類の実施の形態を用いた薄膜トランジスタ構造体の概略図である。
【図２】 本発明によるポリチオフェン類の実施の形態を用いた別の薄膜トランジスタ構造体の概略図である。
【図３】 本発明によるポリチオフェン類の実施の形態を用いた別の薄膜トランジスタ構造体の概略図である。
【図４】 本発明によるポリチオフェン類の実施の形態を用いた別の薄膜トランジスタ構造体の概略図である。
【符号の説明】
１ 薄膜トランジスタ構造体、１２ ポリチオフェン半導体層、１４ 絶縁性誘電体層、１６ 基板、１８ ゲート電極、２０ ソース電極、２２ ドレイン電極、３０ 薄膜トランジスタ構造体、３２ ポリチオフェン半導体層、３４ 絶縁性誘電体層、３６ 基板、３８ ゲート電極、４０ ソース電極、４２ ドレイン電極、５０ 薄膜トランジスタ構造体、５２ ポリチオフェン半導体層、５４ 酸化ケイ素誘電体層、５６ シリコンウエハ、６０ ソース電極、６２ ドレイン電極、７０ 薄膜トランジスタ構造体、７２ ポリチオフェン半導体層、７４ 絶縁性誘電体層、７６ 基板、７８ ゲート電極、８０ ソース電極、８２ ドレイン電極。[0001]
BACKGROUND OF THE INVENTION
The present invention relates generally to organic microelectronic devices, and more particularly, in embodiments, to the use of polythiophenes as active materials in thin film transistors.
[0002]
[Prior art]
Semiconductor polymers such as certain polythiophenes that are useful as active semiconductor materials for thin film transistors (TFTs) have been reported. Many of these polymers have reasonably good solubility in organic solvents, so they can be processed into semiconductor channel layers in TFTs by solution processing such as spin coating, solution casting, dip coating, screen printing, stamp printing, jet printing, etc. can do. The ability to be processed by conventional solution processing makes it easier and less expensive to manufacture than conventional high cost photolithographic processing specific to silicon based devices such as hydrogenated amorphous silicon TFTs. In addition, a transistor made of a polymer material such as polythiophenes with excellent mechanical durability and structural flexibility, called a polymer TFT, is desired. Excellent mechanical durability and structural flexibility are highly desirable for the production of flexible TFTs on plastic substrates. Flexible TFTs are believed to enable the design of electronic devices that typically require structural flexibility and mechanical durability characteristics. The use of plastic substrates with organic or polymer transistor elements can replace conventional rugged silicon TFTs with mechanically more robust and structurally flexible polymer TFT designs. The latter is particularly interesting in that large area devices such as large area image sensors, electronic paper, and other display media as flexible TFTs can be made small and structurally flexible. In addition, the use of polymer TFTs for low-cost microelectronic integrated circuit logic elements such as smart cards and radio frequency data carrier (RFID) tags and memory / storage devices significantly improves their mechanical durability and their use. Longer possible life.
[0003]
[Patent Document 1]
US Pat. No. 6,150,191
[Patent Document 2]
US Pat. No. 6,107,117
[Patent Document 3]
US Pat. No. 5,969,376
[Patent Document 4]
US Pat. No. 5,619,357
[Patent Document 5]
US Pat. No. 5,777,070
[0004]
[Problems to be solved by the invention]
However, many of the semiconductor polythiophenes are not stable when exposed to air because they are oxidatively doped with ambient oxygen and increase conductivity. As a result, devices made from these materials have a high off-current, which reduces the current on / off ratio. Therefore, many of these materials require strict measures to eliminate environmental oxygen and prevent oxidative doping during material processing and device fabrication. This precautionary measure increases the manufacturing cost, which detracts from the appeal of certain polymer TFTs as an economical alternative to amorphous silicon technology, especially for large area devices. These and other disadvantages are avoided or minimized in embodiments of the present invention.
[0005]
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a semiconductor polymer such as polythiophene that is useful for use in a microelectronic device such as a thin film transistor device.
[0006]
[Means for Solving the Problems]
Of the present inventionreferenceThe aspect is as follows. Below2An electronic device comprising polythiophene having the structural formula (I):
[0007]
[Chemical 2]
In the formula, R and R ′ are side chains, A is a divalent linking group, x and y represent the number of unsubstituted thienylene units, z is 0 or 1, and the sum of x and y is Greater than 0, m represents the number of segments, and n represents the degree of polymerization. R and R 'are each independently an electronic device selected from alkyl and substituted alkyl, and A is arylene. R and R 'contain from about 3 to about 20 carbon atoms; R and R ′ are each independently selected from the group consisting of alkyl and alkyl derivatives, wherein the alkyl derivative is an alkoxyalkyl, a siloxy-substituted alkyl, a perhaloalkyl that is a perfluoroalkyl, and a polyether; The group consisting of arylene, wherein A is phenylene, biphenylene, phenanthrenylene, dihydrophenanthrenylene, fluorenylene, oligoarylene, methylene, polymethylene, dialkylmethylene, dioxyalkylene, dioxyarylene, and oligoethylene oxide Electronic device chosen more. R and R 'are each independently a device selected from the group consisting of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and isomers thereof. A device wherein A is arylene having from about 6 to about 40 carbon atoms; R and R ′ are selected from the group consisting of hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl, A is selected from the group consisting of phenylene, biphenylene, and fluorenylene; A device wherein x and y are each independently a number from 0 to about 10, and m is a number from 1 to about 5. N is about 7 to about 5,000, and the number average molecular weight of polythiophene (M) determined by gel permeation chromatography using polystyrene standards.n) Is about 2,000 to about 100,000, and the weight average molecular weight (Mw) Is an electronic device of about 4,000 to about 500,000. A thin film transistor comprising: a substrate; a gate electrode; a gate dielectric layer; a source electrode and a drain electrode; and a semiconductor layer in contact with the source and drain electrodes and the gate dielectric layer, wherein the semiconductor layer comprises polythiophene. R and R ′ are each independently selected from the group consisting of alkyl, alkoxyalkyl, siloxy-substituted alkyl, and perhaloalkyl, and A is phenylene, biphenylene, phenanthrenylene, dihydrophenanthrenylene, fluorenylene, A thin film transistor device selected from the group consisting of oligoarylene, methylene, polymethylene, dialkylmethylene, dioxyalkylene, dioxyarylene, and oligoethylene oxide. N is about 5 to about 5,000, and the number average molecular weight of polythiophene (M) determined by gel permeation chromatography using polystyrene standards.n) Is about 4,000 to about 50,000, and the weight average molecular weight (Mw) Is about 5,000 to about 100,000 thin film transistor devices. A thin film transistor device wherein R and R 'are alkyl containing from about 3 to about 20 carbon atoms; A thin film transistor device wherein A is arylene having from about 6 to about 30 carbon atoms; A thin film transistor device wherein A is arylene having from about 6 to about 24 carbon atoms; A thin film transistor device wherein A is phenylene, biphenylene or fluorenylene; A thin film transistor device with a protective layer.;underRecordingDescribed in 3Structural formula (Represented by 2)PolythiopheWhere n is the degree of polymerization and is 5 to 5000.
[0008]
[Chemical Formula 3]
[Formula 4]
[Chemical formula 5]
A device wherein n is from about 5 to about 5,000; A device wherein n is from about 10 to about 1,000; MnIs about 4,000 to about 50,000, MwIs a device that is about 5,000 to about 100,000. ;Reference modePolythiophene isDescribed in 6, 7A device selected from the group consisting of polythiophenes having the structural formulas (1) to (8).
[0009]
[Chemical 6]
[Chemical 7]
;Reference modePolythiophene isFrom 8 to 11A thin film transistor device selected from the group consisting of polythiophenes having the structural formulas (1) to (14).
[0010]
[Chemical 8]
[Chemical 9]
[Chemical Formula 10]
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;Reference modePolythiophene isDescribed in 12 and 13A thin film transistor device selected from the group consisting of polythiophenes having the structural formulas (1) to (8): wherein n is from about 5 to about 5,000, if necessary.
[0011]
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X, y, and m are 1-3, z is 0 or 1, and the device is a thin film transistor. X, y, and m are 1, z is 0 or 1, and the device is a thin film transistor. X, y, and m are 1, and z is 0 or 1, or x, y, and m are 1, z is 0, and the device is a thin film transistor. The substrate is a plastic sheet that is polyester, polycarbonate, or polyimide; the gate, source, and drain electrodes include gold, nickel, aluminum, platinum, indium titanium oxide, or a conductive polymer; and the gate dielectric layer is A thin film transistor device comprising silicon nitride, silicon oxide, or an insulating polymer. A thin film transistor device in which the substrate is a glass or plastic sheet, the gate, source and drain electrodes each comprise gold and the gate dielectric layer comprises an organic polymer which is poly (methacrylate), poly (vinylphenol). The gate, source and drain electrodes comprise doped organic conducting polymer which is poly (3,4-ethylenedioxythiophene) doped with polystyrene sulfonate, or silver colloidally dispersed in a polymer binder A thin film transistor device manufactured from a conductive ink / paste, wherein the gate dielectric layer is an organic polymer or inorganic oxide particle-polymer composite. ;14Polythiophenes included in
[0012]
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Wherein R and R ′ are side chains, each independently selected from the group consisting of, for example, alkyl and alkyl derivatives, wherein the alkyl derivatives are perhaloalkyls such as alkoxyalkyl, siloxy-substituted alkyl, perfluoroalkyl, Polyethers such as oligoethylene oxide, polysiloxy, etc., A is a divalent linking group, for example, phenylene, biphenylene, phenanthrenylene, dihydrophenanthrenylene, fluorenylene, oligoarylene, methylene, polymethylene, dialkyl Selected from the group consisting of methylene, dioxyalkylene, dioxyarylene, and arylene such as oligoethylene oxide, x and y are each independently an integer selected from 0 to 10, and z is either 0 or 1 And the sum of x and y is 0 Ri large, m is from 1 to about 5 an integer, n represents a degree of polymerization, usually from about 5 to 5,000 or more, more specifically, from about 10 to about 1,000. In both cases, the number average molecular weight of polythiophenes (M) determined by gel permeation chromatography using polystyrene standards.n) Can be, for example, about 2,000 to about 100,000, more specifically about 4,000 to about 50,000, and its weight average molecular weight (Mw) Can be from about 4,000 to about 500,000, more particularly from about 5,000 to about 100,000.
[0013]
Examples of side chains R and R ′ include, for example, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, those having about 1 to about 25 carbon atoms, more specifically about 4 to about 12 carbon atoms. Such as methoxypropyl, methoxybutyl, methoxyhexyl, methoxyheptyl, etc., polyether chains such as polyethylene oxide, perfluoroalkyl (eg, nona Perhaloalkyl such as fluorohexyl, nonafluoroheptyl, pentadecafluorooctyl, tridecafluorononyl, etc.), and polysiloxy chains such as trialkylsiloxyalkyl.
[0014]
The polythiophenes used can contain repeating thienylene units, in which only certain thienylenes have side chains, and the thienylene units are regioregularly arranged on the polythiophene main chain. ing.
[0015]
This polythiophene is substantially stable in the embodiment, and a device can be manufactured using it under ambient conditions. The device also has a high current on / off ratio, is more stable in operation, and its performance is usually known regioregular polythiophenes such as regioregular poly (3-alkylthiophene-2,5-diyl) It does not drop as rapidly as those manufactured from More specifically, the polythiophenes of the present invention are, in embodiments, 3,4-disubstituted-2, which is sandwiched between unsubstituted 2,5-thienylene units and optionally a divalent linking group. Contains repeating segments of 5-thienylene units. The side chain facilitates the induction and promotion of molecular self-assembly of polythiophenes during thin film manufacture. Unsubstituted thienylene units with some rotational freedom and optional divalent linking groups can prevent π conjugation extending along the polythiophene chain and suppress its oxidative doping tendency.
[0016]
According to the above features, the present invention can provide a semiconductor polymer such as polythiophene that is useful for a microelectronic device such as a thin film transistor device.
[0017]
The present invention also provides polythiophenes having a band gap of about 1.5 to about 3 eV determined from the absorption spectrum of the thin film, and these polythiophenes are suitable for use as a thin film transistor semiconductor channel layer material.
[0018]
Furthermore, the present invention provides polythiophenes useful as microelectronic components, which are suitable for common organic solvents such as dichloromethane, tetrahydrofuran, toluene, xylene, mesitylene, chlorobenzene, etc. It has a solubility of 1% by weight or more and can therefore be processed economically by solution processing such as spin coating, screen printing, stamp printing, dip coating, solution casting, jet printing and the like.
[0019]
Another feature of the present invention is that it has a polythiophene channel layer and the conductivity of the layer is 10-6~ About 10-9The provision of electronic devices such as thin film transistors that are S / cm (Siemens / centimeter).
[0020]
Yet another feature of the present invention is the provision of polythiophenes and devices using the same, which devices exhibit excellent resistance to the adverse effects of oxygen, i.e., the device has a relatively high current on / off ratio. Its performance is usually shown to be similar to that produced from regioregular polythiophenes, such as regioregular poly (3-alkylthiophene-2,5-diyl), without abrupt or minimal degradation. Degree.
[0021]
Another feature of the present invention is that the polythiophenes have special structural characteristics that allow the molecules to self-arrange under appropriate processing conditions and that the structural characteristics also improve the stability of device performance. Is an offer. Appropriate molecular arrangements form higher order molecular structure arrangements in the thin film and efficiently move charge carriers to enable high electrical performance.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
The thin film transistor in this embodiment includes:RecordingDescribed in 15Structural formula (Represented by 2)PolythiopheWherein n is the degree of polymerization and is characterized by being 5 to 5000. PoExamples of lithiophenesTheBelowFrom 15 to 18.
[0023]
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Embedded image
Embedded image
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With reference to structural formula (I), the polythiophenes include 3,4-disubstituted-2,5-thienylene units, unsubstituted 2,5-thienylene units, and optionally a divalent linking group. The position regularity segment is included. The regioregularity of the side chains in polythiophene (I) (see structural formulas (1) to (14)) induces molecular self-alignment during the production of the thin film under appropriate processing conditions. It is believed that highly organized microstructures can be made. Higher order microstructures in the semiconductor channel layer of the thin film transistor improve transistor performance. These polythiophenes form a strong intramolecular π-π stack when a thin film with a thickness of about 10 to about 500 nm is formed from a solution dissolved in an appropriate solvent system, and become conductive and efficiently transfer charge carriers. It is thought that. Since the unsubstituted thienylene moiety in (I) has some degree of rotational freedom, it prevents the π conjugation spreading in the molecule of (I) to such an extent that oxidative doping is sufficiently suppressed. Thus, the polythiophenes are stable under ambient conditions, and devices made from these polythiophenes are more functional than regioregular polythiophenes such as regioregular poly (3-alkylthiophene-2,5-diyl) Is more stable. Even without protection, devices made from polythiophenes of structural formula (I) are stable in their embodiments, usually for weeks to months, for example about 3 to about 12 weeks. On the other hand, a device using regioregular poly (3-alkylthiophene-2,5-diyl) degrades in a few days, for example, in less than 5 days, when exposed to ambient oxygen. Devices made from the polythiophenes of this application also have a high current on / off ratio, and their performance has strict operational precautions to eliminate ambient oxygen during material preparation, device manufacturing, and evaluation. Even without it, it does not change as rapidly as that of poly (3-alkylthiophene-2,5-diyl). Materials that are stable to oxidative doping are particularly useful in the manufacture of low cost devices. Because this material is more stable, it usually does not need to be handled in a strictly inert atmosphere, so the manufacturing process is simpler and less expensive, and the process can be a simple large-scale manufacturing process. .
[0024]
In embodiments, the polythiophenes are soluble in common coating solvents such as about 0.1% by weight in solvents such as dichloromethane, 1,2-dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, chlorobenzene and the like. More particularly, it has a solubility of about 0.5 to about 15% by weight. Further, when this polythiophene is processed into a semiconductor channel layer of a thin film transistor device, a stable conductivity is obtained. For example, according to a general 4-probe conductivity measurement method, about 10-9~ About 10-6S / cm, more specifically about 10-8~ About 10-7S / cm.
[0025]
The polythiophenes of the present invention can be prepared by the polymerization of appropriately assembled monomers, such as trithiophene monomers. For example, to prepare exemplary polythiophenes (Ia) and (Ib) according to Scheme 1, 2,5-bis (2-thienyl) -3,4-di-R-thiophene (IIa), or 2,5 -Bis (5-bromo-2-thienyl) -3,4-di-R-thiophene (IIb) is used. Since the monomers (IIa) and (IIb) each have two side chains on the central thienylene unit, the polythiophenes (Ia) and (Ia) in which the side chains are arranged regioregularly on the respective polythiophene main chains upon polymerization. (Ib). Unlike the preparation of regioregular polythiophenes such as poly (3-alkylthiophene-2,5-diyl), which requires a regioregular coupling reaction, the polythiophenes of the present invention have no regioregular complexity. It can be prepared by a usual polymerization method. Specifically, (Ia) is FeClThreeNi (dppe) Cl from monomer (IIa) by treatment with oxidative coupling polymerization mediated by or from Reike zinc2It can be prepared from monomer (IIb) by adding a catalyst. On the other hand, polythiophene (Ib) can be easily obtained from (IIb) by a Suzuki coupling reaction with an appropriate arylene boronate.
[0026]
Embedded image
Specifically, the polymerization of (IIa) is carried out in a stream of dry air with 1 mole of (IIa) dissolved in a chloride solvent, eg chloroform.ThisAbout 1 to about 5 molar equivalents of anhydrous FeCl3Can be added to the chloroform suspension. The resulting mixture is reacted at a temperature of about 25 to about 50 ° C. for about 30 minutes to about 48 hours in a dry air stream or slowly passing a bubble of dry air through the reaction mixture. After the reaction, the reaction mixture is washed with water or dilute aqueous hydrochloric acid, stirred with dilute aqueous ammonia, then washed with water, and then precipitated from methanol or acetone to isolate the polymer product. In the Reyke zinc method, 10 mmol equivalent of (IIb) dissolved in anhydrous tetrahydrofuran was added dropwise with good stirring over 20 to 40 minutes to an anhydrous tetrahydrofuran suspension of Reike Zn immediately after preparation of 11 mmol equivalent. The resulting mixture is then allowed to react at room temperature (about 22 to about 25 ° C.) for about 30 minutes to about 2 hours. Subsequently, about 0.1 mmol equivalent of Ni (dppe) Cl.2Is slowly added over about 10 to about 20 minutes and the mixture is then heated at about 40 to about 65 ° C. for 2 to 5 hours. The reaction mixture is then poured into dilute hydrochloric acid-methanol solution with vigorous stirring to precipitate the polymer product. The latter is redissolved in hot tetrahydrofuran and then reprecipitated from dilute ammonia-methanol solution.
[0027]
More specifically, polythiophene (Ib) is obtained from a Suzuki coupling reaction of monomer (IIb) with a suitable arylene boronate. About 2 to about 4 molar equivalents of a toluene solution of equimolar equivalents of monomer (IIb) and arylenediboronate, about 2 to 6 mole percent tetrakis (triphenylphosphine) palladium, and a 1-2 M aqueous solution. About 1-5 mol% of a phase transfer catalyst such as tetrabutylammonium chloride or tricaprylylmethylammonium chloride in an inert atmosphere for about 90 hours. Heat to ° C. After polymerization, the polythiophene product (Ib) is isolated by repeated precipitation from methanol.
[0028]
Various exemplary embodiments of the present invention are shown in FIGS. Here, polythiophenes are used as channel materials in the thin film transistor (TFT) structure.
[0029]
FIG. 1 shows a substrate 16, a metal contact 18 in contact with it (gate electrode), a layer of insulating dielectric layer 14, and two metal contacts 20 and 22 (source and drain) placed on or on top of it. 1 is a schematic view of a thin film transistor structure 10 including an electrode). Between the metal contacts 20 and 22 is a polythiophene semiconductor layer 12.
[0030]
FIG. 2 is a schematic diagram of another thin film transistor structure 30 that includes a substrate 36, a gate electrode 38, a source electrode 40, a drain electrode 42, an insulating dielectric layer 34, and a polythiophene semiconductor layer 32. .
[0031]
FIG. 3 shows a heavily n-doped silicon wafer 56 acting as a gate electrode, a thermally generated silicon oxide dielectric layer 54, a polythiophene semiconductor layer 52, and a source electrode 60 and a drain electrode 62 placed thereon. 1 is a schematic view of a thin film transistor structure 50 including
[0032]
FIG. 4 is a schematic diagram of another thin film transistor structure 70 that includes a substrate 76, a gate electrode 78, a source electrode 80, a drain electrode 82, a polythiophene semiconductor layer 72, and an insulating dielectric layer 74. .
[0033]
In some embodiments of the present invention, a protective layer may be added on each of the transistor structures of FIGS. In the thin film transistor structure of FIG. 4, the insulating dielectric layer 74 can also function as a protective layer.
[0034]
The substrate layer is generally a silicon material containing various suitable forms of silicon, glass plates, plastic films or sheets, etc., depending on the intended application. For a structurally flexible device, for example, a plastic substrate such as polyester, polycarbonate, or polyimide sheet is desirable. The thickness of the substrate is about 10 μm to 10 mm or more, and the detailed thickness is about 50 to about 100 μm, especially for flexible plastic substrates, and about 1 to about 10 mm for rigid substrates such as glass or silicon. .
[0035]
The insulating dielectric layer that is in contact with the semiconductor layer with the gate electrode separated from the source and drain electrodes can generally be an inorganic material film, an organic polymer film, or an organic-inorganic composite film. The thickness of the dielectric layer is, for example, about 10 nm to about 1 μm, and the more detailed thickness is about 100 to about 500 nm. Specific examples of inorganic materials suitable for the dielectric layer include silicon oxide, silicon nitride, aluminum oxide, barium titanate, barium zirconate titanate, etc. Specific examples of organic polymers suitable for the dielectric layer Examples include polyesters, polycarbonates, poly (vinylphenol), polyimides, polystyrene, poly (methacrylates), poly (acrylates), epoxy resins, and the like. Specific examples of inorganic-organic composite materials include: Examples thereof include ultrafine metal oxide particles dispersed in a polymer such as polyester, polyimide, and epoxy resin. The thickness of the insulating dielectric layer is typically about 50 to about 500 nm, depending on the dielectric constant of the dielectric material used. More specifically, since the dielectric material has a dielectric constant greater than or equal to about 3, a suitable dielectric thickness of about 300 nm is desirable capacitance, eg, about 10-9~ About 10-7F / cm2It can be.
[0036]
An active semiconductor layer containing polythiophenes described in this application is placed between the dielectric layer and the source / drain electrodes. The thickness of this layer is usually from about 10 nm to about 1 μm, or from about 40 to about 100 nm. This layer can usually be produced from a solution of the polythiophenes of the present invention by solution processing such as spin coating, casting, screen, stamp, or jet printing.
[0037]
The gate electrode can be a metal thin film, a conductive polymer film, a conductive film made from a conductive ink or paste, or the substrate itself (eg, highly doped silicon). Examples of gate electrode materials include, but are not limited to, aluminum, gold, chromium, indium tin oxide, conductive polymers, conductive ink / paste, and the like. The conductive polymer is poly (3,4-ethylenedioxythiophene) doped with polystyrene sulfonate (PSS- / PEDOT), and the conductive ink / paste is carbon black / graphite or colloidal silver polymer. Dispersed in a binder (for example, ELECTRODAG manufactured by Acheson Colloids Company) or conductive thermoplastic ink filled with silver (manufactured by Noelle Industries). The gate layer can be prepared by vacuum deposition, sputtering of metals or conductive metal oxides, conductive polymer solutions or conductive inks by spin coating, casting, or printing. The thickness of the gate electrode layer is in the range of about 10 nm to about 10 μm, the preferred thickness for the metal thin film is in the range of about 10 to about 200 nm, and for polymer conductors is in the range of about 1 to about 10 μm.
[0038]
The source and drain electrode layers can be manufactured from a material that provides a low resistance ohmic contact to the semiconductor layer. Typical materials suitable for use as source and drain electrodes include those listed as gate electrode materials such as gold, nickel, aluminum, platinum, conductive polymers, conductive inks, and the like. Typical thickness of this layer is, for example, from about 40 nm to about 1 μm, with a more detailed thickness being about 100 to about 400 nm. The TFT device structure comprises a semiconductor channel having a width W and a length L. The semiconductor channel width is about 10 μm to about 5 mm, and the desired channel width is about 100 μm to about 1 mm. The semiconductor channel length is about 1 μm to about 1 mm, and the more detailed channel length is about 5 to about 100 μm.
[0039]
The source electrode is grounded and typically has a bias of about 0 to about −80 volts to collect charge carriers that move through the semiconductor channel when a voltage of about +10 to about −80 volts is applied to the gate electrode. A voltage is applied to the drain electrode.
[0040]
【Example】
a) Device manufacture:
As a basic arrangement of the device under test, the bottom contact type and top contact type thin film transistor structures shown in FIGS. 1 and 3 were used. The bottom contact type test device includes a series of transistor dielectric layers that are pre-patterned with a photographic plate on a glass substrate, and electrodes having a prescribed channel width and length. The gate electrode on the glass substrate was made of chromium with a thickness of about 80 nm. The gate dielectric is about 22 nF / cm2It was 300 nm thick silicon nitride with a capacitance of (nanofarad / square centimeter). Source and drain contacts made of about 100 nm thick gold were vacuum deposited over or on top of the gate dielectric layer. Next, a test polythiophene semiconductor layer having a thickness of about 30 to about 100 nm was applied by spin coating under ambient conditions without taking any measures to prevent exposure to ambient oxygen, moisture, or light. The solution used for the production of the semiconductor layer consisted of 1% by weight of polythiophene dissolved in a suitable solvent and was filtered through a 0.45 μm filter before use. The spin coating was performed at a rotational speed of 1,000 rpm for about 35 seconds. The obtained coated device was dried for 20 hours at 80 ° C. in a vacuum, and then subjected to evaluation.
[0041]
The top contact type test device includes an n-doped silicon wafer and a silicon oxide layer having a thickness of about 110 nm that is thermally generated thereon. While the wafer functions as the gate electrode, the silicon oxide layer acts as the gate dielectric and its capacitance is about 32 nF / cm.2Met. The silicon wafer was first cleaned with methanol, air-dried, and then immersed in a 0.01 M 1,1,1,3,3,3-hexamethyldisilazane dichloromethane solution at room temperature (22-25 ° C.) for 30 minutes. . The wafer was then washed with dichloromethane and dried. A semiconductor polythiophene layer having a thickness of about 30 to about 100 nm was applied onto the silicon oxide dielectric layer by spin coating and dried in a vacuum at 80 ° C. for 20 hours. During device manufacture, no measures were taken to prevent exposure of the material to ambient oxygen, moisture, or light. Next, gold source and drain electrodes were vacuum deposited over the semiconductor polythiophene layer through shadow masks of various channel lengths and widths to produce a series of transistors of various sizes. As a precaution, the manufactured device was stored in a dark place in a dry atmosphere with a relative humidity of about 30% before and after evaluation.
[0042]
b) TFT device characteristics evaluation:
The performance of the field effect transistor was evaluated at ambient conditions in a dark box using a Keithley 4200 SCS semiconductor characterization device. Carrier mobility (μ) is the saturation region (gate voltage, VG<Source-drain voltage, VSD) Was calculated according to the following equation (1).
[0043]
[Formula 1]
ISD= Ciμ (W / 2L) (VG-VT)2 (1)
Where ISDIs the drain current in the saturation region, W and L are the width and length of the semiconductor channel, respectively, and CiIs the capacitance per unit area of the gate dielectric layer and VGAnd VTAre the gate voltage and the threshold voltage, respectively. V of this deviceTIs I in the saturation regionSDFrom the square root ofSD= V of the device obtained by extrapolating 0GIt was calculated from the relationship.
[0044]
The value representing the characteristics of the thin film transistor is its current on / off ratio. This is the gate voltage VGIs the drain voltage VDSaturation source-drain current and the gate voltage VGIs the ratio to the source-drain current when is zero.
[0045]
Comparative example
The above procedure is essentially repeated except that a known regioregular polythiophene, poly (3-hexylthiophene-2,5-diyl) is used, and the bottom contact type device and the top contact shown in FIGS. 1 and 3, respectively. A mold device was manufactured. This material was purchased from Aldrich Chemical and purified by repeating the precipitation from the chlorobenzene solution into methanol three times.
[0046]
The semiconductor polythiophene layer was coated on the device under ambient conditions by spin coating of a 1% by weight regioregular poly (3-hexylthiophene-2,5-diyl) chlorobenzene solution according to the procedure described above. The device was dried in vacuum at 80 ° C. for 20 hours before evaluation. The average characteristic values obtained from five or more transistors for each device are summarized below.
(1) Bottom contact type device (W = 1,000 μm, L = 10 μm)
Mobility: 1 to 2.3 × 10-3cm2/ V. sec
Initial current on / off ratio: 0.8 to 1 × 10Three
Current on / off ratio after 5 days: 5-10
(2) Top contact type device (W = 5,000 μm, L = 60 μm)
Mobility: 1-1.2 × 10-2cm2/ V. sec
Initial current on / off ratio: 1.5 to 2.1 × 10Three
Current on / off ratio after 5 days: 5-10
[0047]
The observed low initial current on / off ratio is that poly (3-hexylthiophene-2,5-diyl) is susceptible to oxidative doping, ie, poly (3-hexylthiophene-2 in the presence of ambient oxygen , 5-diyl) is unstable. The significant decrease in current on / off ratio within only 5 days further supports the severe functional instability of poly (3-hexylthiophene-2,5-diyl) at ambient conditions.
[0048]
Example
(A) Synthesis of poly [2,5-bis (2-thienyl) -3,4-dioctylthiophene] (2)
i) Synthesis of monomer: The monomer used for the preparation of polythiophene (2), 2,5-bis (5-bromo-2-thienyl) -3,4-dioctylthiophene, was synthesized as follows.
[0049]
3,4-Dioctylthiophene: Dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) dissolved in 200 ml of anhydrous diethyl ether in a 500 ml round bottom flask cooled with an ice bath in an inert atmosphere. ) (0.2 g) and 3,4-dibromothiophene (20.16 g, 0.0833 mol) while stirring well, 2M octylmagnesium bromide (100 ml, 0.2 mol) in anhydrous diethyl ether The solution was added. The nickel complex immediately reacted with the Grignard reagent and the resulting reaction mixture was allowed to warm to room temperature. The exothermic reaction started within 30 minutes and diethyl ether began to gently reflux. After further stirring for 2 hours at room temperature, the reaction mixture was refluxed for 6 hours, cooled in an ice bath and hydrolyzed with 2N aqueous hydrochloric acid. The organic layer was separated, washed with water, then with brine, washed again with water and then dried over anhydrous sodium sulfate. After evaporation of the solvent, the residue was distilled under reduced pressure through a Kugelrohr device to give 21.3 g of 3,4-dioctylthiophene as a colorless liquid.
1H-NMR (CDClThree): Δ 6.89 (s, 2H), 2.50 (t, J = 7.0 Hz, 4H), 1.64-1.58 (m, 4H), 1.40-1.28 (m, 20H) ), 0.89 (t, J = 6.5 Hz, 6H)
13C-NMR (CDClThree): Δ 142.1, 119.8, 31.9, 29.6 (2C), 29.5, 29.3, 28.8, 22.7, 14.1.
[0050]
2,5-dibromo-3,4-dioctylthiophene: 3,4-dioctylthiophene (3.6 g, 11.7 mmol) dissolved in a mixture of 30 ml dichloromethane and 10 ml acetic acid in a 100 ml round bottom flask To this well stirred N-bromosuccinimide (4.6 g, 25.7 mmol) was added. When the reaction state was observed by thin layer chromatography, it was completed in about 35 minutes. The mixture was diluted with 160 ml of dichloromethane and filtered to remove succinimide. The filtrate was washed with 2N aqueous sodium hydroxide solution and then twice with water (2 × 100 ml). After drying over anhydrous sodium sulfate, the solvent was removed to obtain 5.4 g of 2,5-dibromo-3,4-dioctylthiophene as a pale yellow liquid.
1H-NMR (CDClThree): Δ 2.50 (t, J = 7.0 Hz, 4H), 1.52-1.28 (m, 24H), 0.89 (t, J = 6.5 Hz, 6H)
[0051]
2,5-bis (2-thienyl) -3,4-dioctylthiophene: 2,5-dibromo dissolved in anhydrous tetrahydrofuran (50 ml) in a 250 ml round bottom flask in a dry box in an inert atmosphere A mixture of −3,4-dioctylthiophene (4.2 g, 9.0 mmol) and 2- (tributyltin) thiophene (7.4 g, 19.8 mmol) was added to Pd (PPhThree)2Cl2(0.15 g, 0.2 mmol) was added. The mixture was then refluxed for 12 hours and the solvent was distilled off. The crude product thus obtained was purified by flash chromatography on silica gel using hexane as the eluent and 3.1 g of 2,5-bis (2-thienyl) -3,4- Dioctylthiophene was obtained.
1H-NMR (CDClThree): Δ 7.31 (dd, J = 3.2, 0.5 Hz, 2 H), 7.13 (dd, J = 2.2, 0.5 Hz, 2H), 7.06 (dd, J = 2) .2, 4.5 Hz, 2H), 2.68 (dd, J = 7.6, 7.6 Hz, 4H), 1.59-1.53 (m, 4H), 1.42-1.27 ( m, 20H), 0.91 (t, J = 6.5 Hz, 6H)
[0052]
2,5-bis (5-bromo-2-thienyl) -3,4-dioctylthiophene: 2,5 dissolved in N, N-dimethylformamide (30 ml) in a 100 ml round bottom flask cooled in an ice bath While stirring a solution of -bis (2-thienyl) -3,4-dioctylthiophene (3.6 g, 7.6 mmol), N-bromosuccinimide (2.8 g, 15.7 mmol) was added thereto. After the addition, the mixture was allowed to warm slowly to room temperature. When the reaction was observed by thin layer chromatography, the reaction stopped after 3 hours. The resulting mixture was diluted with hexane (170 ml) and washed 3 times with 100 ml water. The organic layer was separated, dried over anhydrous sodium sulfate and evaporated in vacuo to give the crude product. This was purified by flash chromatography on silica gel using hexane as the eluent to give 2.5 g of 2,5-bis (5-bromo-2-thienyl) -3,4-dioctylthiophene.
1H-NMR (CDClThree): Δ 7.06 (d, J = 3.5 Hz, 2H), 6.86 (d, J = 3.5 Hz, 2H), 2.62 (dd, J = 7.3, 7.3 Hz, 4H) , 1.55-1.49 (m, 4H), 1.41-1.28 (m, 20H), 0.89 (t, J = 6.5 Hz, 6H)
13C-NMR (CDClThree); Δ 140.6, 137.4, 130.2, 129. 3, 126.2, 112.0, 31.9, 30.8, 29.8, 29.2 (2C), 28.1, 22.7, 14.2.
[0053]
Poly [2,5-bis (2-thienyl) -3,4-dioctylthiophene] (2): 2,5-bis (5-bromo-2-thienyl) -3,4 dissolved in anhydrous tetrahydrofuran (10 ml) -An inert atmosphere while stirring well a solution of diketylthiophene (2.46 g, 3.9 mmol) in a fresh tetrahydrofuran (20 ml) suspended in reiki Zn (0.28 g, 4.29 mmol) Added dropwise in, and the mixture was allowed to react for 45 minutes at room temperature. Next, Ni (dppe) Cl suspended in anhydrous tetrahydrofuran (35 ml).2(0.021 g, 0.04 mmol) was added carefully. The reaction mixture was heated at 60 ° C. for 3 hours and then poured into a 2N hydrochloric acid-methanol solution. The precipitated polythiophene product was filtered, redissolved in 70 ml of hot tetrahydrofuran and precipitated from a 2N ammonia-methanol solution. This operation was repeated twice to remove the acid and oligomer. 1.6 g of M after drying in vacuum at room temperaturew41,900, MnA poly [2,5-bis (2-thienyl) -3,4-dioctylthiophene] (2) having a temperature of 11,800 K and Tm of 180 ° C. was obtained.
1H-NMR (CDClThree): Δ 7.30, 7.13, 7.05, 2.73, 1.59, 1.45, 1.29, 0.89
13C-NMR (CDClThree): Δ 140.4, 136.7, 135.1, 129. 8, 126.4, 123.9, 31.9, 30.7, 29.9, 29.3, 28.3, 22.7, 14.2.
[0054]
Two test devices, one bottom contact type and one top contact type arrangement, respectively illustrated in FIGS. 1 and 3, were manufactured using the polythiophene according to the above-described manufacturing procedure. The device was dried in vacuum at 80 ° C. for 20 hours prior to evaluation. The average characteristic values obtained from five or more transistors for each device are summarized below.
(1) Bottom contact type device (W = 1,000 μm, L = 10 μm)
Mobility: 3.4 × 10-Four~ 1.3 × 10-3cm2/ V. sec
Initial current on / off ratio: 0.8 to 1.3 × 10Four
Current on / off ratio after 5 days: 5.0 to 7.0 × 10Three
(2) Top contact type device (W = 5,000 μm, L = 60 μm)
Mobility: 1.3-3.1 × 10-3cm2/ V. sec
Initial current on / off ratio: 1.5 to 2.6 × 10Five
Current on / off ratio after 5 days: 1.1 to 2.0 × 10Five
Current on / off ratio after 30 days: 8.0 to 9.5 × 10Four
[0055]
Since the initial current on / off ratio is large and the current on / off ratio declines slowly over time, it was shown that the polythiophene semiconductor layer of the embodiment of the present invention is stable.
[Brief description of the drawings]
FIG. 1 is a schematic diagram of a thin film transistor structure using an embodiment of polythiophenes according to the present invention.
FIG. 2 is a schematic diagram of another thin film transistor structure using an embodiment of polythiophenes according to the present invention.
FIG. 3 is a schematic diagram of another thin film transistor structure using an embodiment of polythiophenes according to the present invention.
FIG. 4 is a schematic diagram of another thin film transistor structure using an embodiment of polythiophenes according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Thin-film transistor structure, 12 Polythiophene semiconductor layer, 14 Insulating dielectric layer, 16 Substrate, 18 Gate electrode, 20 Source electrode, 22 Drain electrode, 30 Thin-film transistor structure, 32 Polythiophene semiconductor layer, 34 Insulating dielectric layer, 36 Substrate, 38 gate electrode, 40 source electrode, 42 drain electrode, 50 thin film transistor structure, 52 polythiophene semiconductor layer, 54 silicon oxide dielectric layer, 56 silicon wafer, 60 source electrode, 62 drain electrode, 70 thin film transistor structure, 72 polythiophene Semiconductor layer, 74 insulating dielectric layer, 76 substrate, 78 gate electrode, 80 source electrode, 82 drain electrode.
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| US10/042,356 US6621099B2 (en) | 2002-01-11 | 2002-01-11 | Polythiophenes and devices thereof |
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| NO314525B1 (en) * | 1999-04-22 | 2003-03-31 | Thin Film Electronics Asa | Process for the preparation of organic semiconductor devices in thin film |
| GB0028867D0 (en) * | 2000-11-28 | 2001-01-10 | Avecia Ltd | Field effect translators,methods for the manufacture thereof and materials therefor |
-
2002
- 2002-01-11 US US10/042,356 patent/US6621099B2/en not_active Expired - Lifetime
-
2003
- 2003-01-10 DE DE60308738T patent/DE60308738T2/en not_active Expired - Lifetime
- 2003-01-10 EP EP03000412A patent/EP1329474B1/en not_active Expired - Lifetime
- 2003-01-14 JP JP2003006210A patent/JP4530616B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08508311A (en) * | 1993-03-31 | 1996-09-03 | シス バイオ インターナショナル | Conductive polymer / nucleotide copolymer, method for producing the same and use thereof |
| JP2000506914A (en) * | 1996-03-06 | 2000-06-06 | ビーエーエスエフ アクチェンゲゼルシャフト | Substituted polythiophenes, their production and their use |
| JP2003261655A (en) * | 2002-01-11 | 2003-09-19 | Xerox Corp | Polythiophenes and device using these |
Also Published As
| Publication number | Publication date |
|---|---|
| US20030136958A1 (en) | 2003-07-24 |
| JP2003264327A (en) | 2003-09-19 |
| DE60308738T2 (en) | 2007-01-18 |
| EP1329474B1 (en) | 2006-10-04 |
| DE60308738D1 (en) | 2006-11-16 |
| EP1329474A1 (en) | 2003-07-23 |
| US6621099B2 (en) | 2003-09-16 |
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